Colored photographic materials and method of producing them



Patented Mar. 30, 1937 UNITED STATES COLORED PHOTOGRAPHIC MATERIALS AND METHOD OF PRODUCING THEM Bla Gaspar, Brussels, Belgium No Drawing. Application April 19, 1934, Serial 13 Claims.

This invention relates to a. method of producing colored photographic materials.

It is already known for the purpose of producing color photographs to incorporate dye- 5 stuffs in photographic layers, and to fix these by a mordanting process or by the formation of a deposit. In this connection, however, it has been found that various dyestuffs reveal the tendency to separate again subsequently from the mordant. Beyond this, the inorganic salts proposed for this purpose are very disturbing in the layer, as the same may readily react with the photographic bath or take efiect on the silver halide.

It has been found that diffusion of the dyestuffs in the layer may be prevented to a very considerable extent if salts of the fast acid dyestuffs, and more particularly of the sulphonic acids of these dyestuffs, are introduced into the layer with nitrogenous organic bases. These substances also have no detrimental effect on the silver halide.

The salts in question may be incorporated in finished state in the layers or emulsions in fine suspension or by way of addition in a suitable solvent, for example alcohol, or these deposits may be produced in the layer itself by double decomposition. These non-diffusing salts of the dyestufi may be incorporated in those layers,

which consist of a plurality of part-layers poured one on to the other, or of a plurality of particles, such as result from the known re-emulsifying action of differently colored emulsions. may also be formed by applying, atomizing or impressing the dyestufif on to a colloidal layer, whereby there is employed either a solution of the dyestufi salts, or the same may be employed together with the organic bases for coloring the arrangements as described, or the dyestuif deposit may be formed in the layer itself by way of double decomposition. This method of fixing dyestufis may also be employed for other purposes, for example in the transfer' method, in which, for example, an organic base is introduced into the colloid used for the transfer, and an insoluble non-diffusing salt of the dyestuff there formed after the transfer has taken place. In this method the transfer images are extremely 0 sharp, owing to prevention of the diffusion. This method is also extremely useful for the production of antihalation layers.

Layers containing, for example, dyes, which may be removed entirely from the gelatin by washing, may be applied to the emulsion car- They In Germany April 19, 1933 'rier on the front or the rear side of'a film or plate or immediately above or below the emulsion.

In my prior application 645,312 dated Decembe r 1, 1932, matured into Patent No. 2,046,067, of June 30, 1936, I have already described a meth- I 5 od as set forth in the'above making use of a difficultly soluble non-diffusing salt of an organic base, which is not a dyestuii, and an acid dyestufl'.

The invention relates to an additional devel- 10 opment of this .process. It has been found that the quaternary salts of heterocyclic bases are very suitable for the purpose in question. These salts are remarkable for extremely good solubility in water, and do not have a detrimental 15 effect of any kind in the emulsion. The salts of these bases result together with the acid dyestuifs in salts which are soluble only with extreme difllculty.

An additional advantage resides in the fact that the insoluble dyestufl salts may be produced in the photographic emulsion directly, in which connection a subsequent washing is usually unnecessary.

Suitable salts are the quaternary salts of the higher homologues of pyridine, for example alkylnaphthoquinolinium' salts, anthraquinolinium salts, thiazolium salts, benzothiazolium and naphthothiazolium salts, whereby the 3-4 carbon atoms of the pyridine ring may be substituted 30 by sulphur, selenium or oxygen. Othersuitable substances are halogen alkylates, perchlorates, alkyl sulphates and alkyl toluene sulphonates.

It has been found that alkyl sulphates are particularly suitable. 35

Example 1.-A silver bromide emulsion containing 2 grammes Diamine Pure Blue FF per litre has admixed therewith, prior to pouring, a solution comprising .5 gramme l-ethylquinoline ethylsulphate in 20 cm water.

Example 2.To an emulsion colored with Chloramine Light Red 73L at the rate of 3 grammes per litre there is added a solution of .5 gramme 1-methylbetanaphthoquinoline perchlorate in cm water. 45

What I claim as new and desire to secure by Letters Patent is:

1. A method of producing colored photographic materials which comprises producing in a light sensitive silver halide emulsion a substantially water insoluble, non-diffusing compound by the addition of a quaternary salt of a substantially colorless organic base and an acid dyestufi, and pouring the said emulsion having the dyestuffs incorporated therein on a support.

2. A method of producing colored photographic materials which comprises producing in a light sensitive silver halide emulsion a substantially water insoluble, non-diflusing compound by the addition oi! aikylsulphates ora quaternary organic base and anacid dyestufl, and pouring the said emulsion having the dyestui! incorporated therein on a support.

8. A method of producing colored photographic 1o materials which comprises producing in a colloidal solution a substantially water insoluble, non-ditiusing compound by the addition of a substantially colorless quaternary salt of an organic base and an acid dyestufl. pouring a light sensitive silver halide emulsion on a support, and pouring the said colloidal solution on the said emulsion.

4. A method of producingcolored photographic materials which comprises producing in a colloidal solution a substantially water uble,,

non-diiiusing compound by the addi on of a substantially'colorlew quaternary salt oian organic base and an acid dyestumpouringthe said colloidal solution on a support, and pouring a light sensitive silver halide emulsion on the said colloidal solution. a

5. A method of producing colored photographic materials which comprises producing in a light sensitive silver halide colloidal emulsion by double decomposition a substantially water in- 80 soluble,'non'-diflusing compound by the addition oi a substantially colorless quaternary salt of organic base and anacid dyestufl. and applying the said emulsion and dyestui! to a support.

6. A method of producing colored photographic to materials which comprises producing-in a light sensitive silver hdide emulsion' a substantially water insoluble, non-diffusing compound by the addition of quaternary salts of the higher homologues of pyridine and an acid dyestuil, and pouring the said emulsion having the dyestuil' incorporated therein ona support.

7. A method of producing colored photographic materials which comprises producing in a light sensitive silver halide emulsion a substantially as water insoluble, non-diflusing compound by the addition of any of the following quaternary salts of organic bases: alkyl halides, perchlorates, al-

lryltoluene sulphonates, alkylsulphates, and an acid dyestuii', and pouring the said emulsion having the dyestui! incorporated therein on a sup- P rt. 4

8. In a method of producing colored light sensi- 5 tive silver halide colloids, the step which consists in adding to the said colloids a quaternary salt of a substantially colorless'organimbasefind an acid dyestui! to torus substantially water insoluble non-diflusing 10 9. In a method of producing colored photographic materials, the steps which comprise adding to the light sensitive silver halide emulsion a quaternary salt of a substantially colorless organic base. applying the said emulsion to a sup-- 1:; portandthereuponapplyinganacijddyestuflto form a substantialhr water insoluble non-diflusing compound.

IO A photographic material comprising. a colored. light sensitive silver halide emulsion layer containing a substantially water insoluble; nondiflusing compound ohan acid dyestuilwith a substantially mlorless salt of a quaternary orsonic base. A

' 11. A photographic material comprising -a colored light sensitive silver halide emulsion layer containing a substantially water insoluble, nondiilusing compound produced by the addition of an acid dyestuii and a substantially colorless salt of a quaternary organic base to the light ,30 sensitive emulsion.-

12. A photographic material comprising a light sensitive silver halide-emulsion layer containing a substantially water insoluble, non-diflusing compound oi an acid dyestuil' and a quaternary ,35 

